Activated carbon (AC) supported Cu catalysts are employed to study the influence of surface oxygenated groups on the formation of active Cu species and the catalytic activity of Cu/AC catalyst for oxidative carbonylation of methanol to dimethyl carbonate (DMC). The AC supports are thermal treated under different temperatures in order to adjust the levels of surface oxygenated groups. The AC supports are characterized by BET, TAD-MS and XRD, and the Cu/AC catalysts are characterized by BET, XRD, TEM, XPS, AAS, CH3OH-TPD and N2O chemisorption. The results show that as the treatment temperature is below 800 degrees C,the BET surface area of the corresponding AC supports are nearly unchanged and close to that of the original AC (1529.6 m(2)/g). But as the thermal treatment temperature is elevated from 1000 to 1600 degrees C, the BET surface area of AC supports gradually decreases from 1407.6 to 972.2 m(2)/g. After loading of Cu, the BET surface area of copper catalysts is in the range of 834.4 to 1545.3 m(2)/g, which is slightly less than that of the respective supports. When AC is thermal treated at 400 and 600 degrees C, the unstable carboxylic acid and anhydrides groups are selectively removed, which has weakened the mobility and agglomeration of Cu species during the calcination process, and thus improve the Cu species dispersion over AC support. But as the treatment temperature is elevated from 600 degrees C to 1200 degrees C, the Cu species dispersion begins to decline suggesting further removal of stable surface oxygenated groups is unfavorable for Cu species dispersion. Moreover, higher thermal treatment temperature (above 1200 degrees C) promotes the graphitization degree of AC and leds to the decrease of Cu loading on AC support. Meanwhile, the removal of surface oxygenated groups by thermal treatment is conducive to the formation of more pi-sites, and thus promote the reduction of Cu2+ to Cu+ and Cu-0 as active centers. The specific surface area of (Cu+ + Cu-0) is improved by thermal treatment of AC, however, the space time yield of DMC on unit specific surface area of (Cu+ + Cu-0) is in the range of 23.1-49.1 mg h(-1) m(-2), which is much less than that (77.6 mg h(-1) m(-2)) of the original catalyst. The possible reason is that the removal of surface oxygenated groups results in AC support transforms from hydrophilicity to hydrophobicity, which is detrimental for the adsorption of CH3OH resulting in the decreased local concentration of CH3OH on active Cu species. (C) 2016 Elsevier B.V. All rights reserved.